Gem-dinitroalkanediamines



United States Patent 3,000,952 GEM-DINITROALKANEDIAM Marvin H. Gold,Pasadena, Calif., and Levonna Herzog, Mountain View, NJ., assignors toAeroiet-General Corporation, Azusa, Califi, a corporation of Ohio NoDrawing. Filed Apr. 11, 1957, Ser. No. 652,305 5 Claims. (Cl. 260-583)This invention relates to new compositions of matter and methods forproducing the same, and is related in particular to genn'nal dinitroalkane diam-inc compounds having the general formula:

wherein A is a lower alkylene radical.

This application is a continuation-in-part of our copending UnitedStates patent application Serial No. 428,790, filed May 10, 1954, nowabandoned, which was a continuation-impart of our copending UnitedStates patent application Serial No. 210,626, filed February 12, 1951,now abandoned.

The diamines of this invention can be converted to their correspondingdiols by the action of nitrous acid. The diols thus produced are usefulin the preparation of polyurethane propellants, as disclosed inassignees eopending United States patent application Serial No. 422,-649, filed April 12, 1954, now abandoned.

The diamines of this invention also react with betageminal dinitroalcohols such as trinitroe-th-anol to form valuable high explosivecompositions, as disclosed in assignees cope-nding United States patentapplication Serial No. 421,984, filed April 8, 1954-, now abandoned. Thehigh explosives thus formed can be used in any conventional explosivemissile, projectile, rocket, or the like, as the main explosive charge.An example of such a missile is disclosed in United States Patent No.2,470,- 162, issued May 17, 1949. One way of using the high explosivesof this invention in a device such as that disclosed in United StatesPatent No. 2,470,162, is to pack the crystalline explosive in powderform into the warhead of the missile. Alternatively, the crystals can befirst pelletized and then packed. A charge thus prepared is sutficientlyinsensitive to withstand the shock entailed in the ejection of a shellfrom a gun barrel or from a rocket launching tube under the pressuredeveloped from ignition of a propellant charge, and can be caused toexplode on operation of an impactor time fuse-mechanism firing adetonating explosive such as lead azide or mercury fulminate.

The compositions of this invention are conveniently prepared byhydrolyzing a geminal dinitroalkane dicarbamate in the presence of astrong mineral acid and subsequently neutralizing the resultant diaminesalt with an alkali or alkaline earth metal base in accordance with thegeneral reaction scheme set forth below:

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N 0 NH4|ACH:|$CH|A-NHr 0: wherein R is an alkyl radical, A is analkylene radical and X is the anion of a strong mineral acid.

The following examples are provided to more clearly illustrate theinvention. It is to be understood that these examples are presentedmerely as a means of illustration and are not intended to limit thescope of the invention to the particular conditions set forth therein.

EXAMPLE I Preparation of dimethyl-3,3-dinitro-1,5-pentaned'icarbam are Amixture of one mole of 3,3-dinitro-l,5-pentane diisocyanate and 1.5liters of methanol was placed in a flask equipped wtih a refluxcondenser. The alcohol reacted with the diisocyanate thus generatingsuflicient heat to bring the reaction mixture to reflux temperature. Thereaction was allowed to proceed until substantially complete. Excessivemethanol was removed by distillation and crystals ofdimethyl-3,3-dinitro-L5-pentanedicarbamate were collected on a Buchnerfunnel and recrystallized from chloroform. Pure dimethyl-3,3-dinitro-LS-pentanedicarbamate was obtained as a white crystalline solid having amelting point of approximately 114 C. The yield was about to oftheoretical.

EXAMPLE 11 Preparation of 3,3-dinitro-I,5-pentanediamine dihydrochlorideand 235 C.

EXAMPLE III Preparation of 3,3-dinilro-I,5-pentanediamine To astoichiometrically equivalent solution of sodium hydroxide in alcoholwas added 3,3-dinitro-l,5-pentanediamine dihydrochloride and the wholethen shaken. The resultant free diamine was separated from the mixtureby filtration, as a colorless solid having a melting point of about73-74 C.

The free diamine was further characterized by the preparation of thedibenzoyl and diacetyl derivatives by the reaction with benzoyl chlorideand acetyl chloride. The dibenzamide melted at 144-145 C. and thediacetamide melted at 147 C.

The reaction temperature is non-critical in the practice of thisinvention, the only effect of temperature changes being correspondingincreases or decreases in the rate of reaction. As a matter ofconvenience, it is preferred to conduct the hydrolysis reaction atreflux temperature.

The diisocyanates employed as starting materials in this invention, suchas 3,3-dinitro-L5-pentane diisocyanate, are prepared by reacting agem-dinitro diacid halide, such as 4,4-dinitroheptanedioyl chloride,with an azide of an alkali or alkaline earth metal, such as sodi- 3 umazide, and heating the resulting product to effect rearrangement to thedesired diisocyanate, as more fully disclosed in our copending UnitedStates patent application Serial No. 623,728, filed November 16, 1956.

By merely selecting an appropriate diisocyanate, such as4,4-dinitro-l,7-heptane diisocyanate, and 5,5-dim'tro- 1,9-nonanediisocyanate and proceeding in accordance with the examples given above,a wide variety of homologues of this invention can be obtained, such as4,4-dinitro-1,7-hepta.nediamiue, 5,5-dinitro-L9-nonanediamine, etc.

We claim:

1. As new compositions of matter the geminal dinitroalkanediaminecompounds having the formula:

wherein A is a lower alkylene radical.

2. As a composition of matter, 3,3-dinitro-L5-pentanediamine having thestructural formula:

NHr-CHr-CHg-C-Hg-CHg-NH:

B. The method of preparing geminal dinitroalkane-diamine compoundshaving the formula:

N0: NBrACHr+-CH1-ANH N02 which comprises hydrolyzing a geminaldinitroalkanedicarbamate having the structural formula:

0 N0: 0 l! RO- NHA--CHr-|--CHr-A-NH OR wherein A is a lower alkyleneradical and R is a lower alkyl radical, in the presence of a strongmineral acid, and subsequently neutralizing the resultant diamine salt.

4. The method of preparing 3,3-dinitro-L5-pentane-diamine whichcomprises hydrolym'ng a dialkyl-3,3-dinitro- LS-pentane-dicarbamate inthe presence of a strong mineral acid and subsequently neutralizing theresultant diacid salt.

5. The method of preparing 3,3-dinitro-l,5-pentanediamine whichcomprises hydrolyzing dimethyl-3,3-dinitro-LS-pentanedicarbamate in thepresence of hydrochloric acid and subsequently neutralizing theresultant dihydrochloride salt with sodium hydroxide.

References Cited in the file of this patent Herzog et al.: Am. Chem.Soc. Abstracts of Papers, 118th Meeting, page 25N (1950).

Wertheim: Textbook of Organic Chemistry, page 352 (1951), 3rd. edition.

1. AS NEW COMPOSITIONS OF MATTER THE GEMINAL DINITROALKANEDIAMINE COMPOUNDS HAVING THE FORMULA: 